CN107533294A - Liquid solder mask agent composition and printed substrate - Google Patents

Liquid solder mask agent composition and printed substrate Download PDF

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Publication number
CN107533294A
CN107533294A CN201680024471.3A CN201680024471A CN107533294A CN 107533294 A CN107533294 A CN 107533294A CN 201680024471 A CN201680024471 A CN 201680024471A CN 107533294 A CN107533294 A CN 107533294A
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China
Prior art keywords
solder mask
compound
epoxide
composition
weight
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CN201680024471.3A
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CN107533294B (en
Inventor
酒井善夫
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Goo Chemical Industries Co Ltd
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Goo Chemical Industries Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/285—Permanent coating compositions
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
    • H05K3/3452—Solder masks
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0274—Optical details, e.g. printed circuits comprising integral optical means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/20—Details of printed circuits not provided for in H05K2201/01 - H05K2201/10
    • H05K2201/2054—Light-reflecting surface, e.g. conductors, substrates, coatings, dielectrics

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Materials For Photolithography (AREA)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The present invention solves the problems, such as to provide liquid solder mask agent composition, although composition includes powdered hydroquinone epoxy compound, the liquid solder mask agent composition can also be formed as the glossy solder mask with very smooth surface.The liquid solder mask agent composition includes containing carboxy resin (A), thermal curable components (B), photopolymerizable component (C) and Photoepolymerizationinitiater initiater (D).The thermal curable components (B) include the Powder epoxy compound (B11) represented by formula (1).

Description

Liquid solder mask agent composition and printed substrate
Technical field
The present invention relates to liquid solder mask agent composition and printed substrate, and in particular to：With photocurable and can be with The liquid solder mask agent composition to be developed with alkaline solution；With the print of the solder mask including being formed by the liquid solder mask agent composition Brush wiring board.
Background technology
In recent years, the method as the formation solder mask on the printed substrate for consumer applications and industrial use, The liquid solder mask agent composition with excellent resolution ratio and dimensional accuracy that widely using can be developed with alkaline solution substitutes Silk screen print method, to increase the wiring density on printed substrate.
Sometimes epoxide is included in solder mask composition, so that solder mask composition also obtains in addition to photocurable Obtain thermosetting.In patent document 1, hydroquinone epoxy compound is disclosed as the one kind that may be embodied in solder mask composition Epoxide.Have by the coating solder mask composition comprising hydroquinone epoxy compound being applied in substrate to be formed Good alkali-developable and low adherence.There is good flexibility, hot-cracking resistance by the solder mask for making curing of coatings to be formed And heat resistance.
However, there are the following problems：When forming welding resistance by the solder mask composition comprising powdered hydroquinone epoxy compound During layer, the glossiness and surface smoothness of solder mask reduce.If the surface smoothness of solder mask is low, when transport includes welding resistance During the printed substrate of layer, there may be slide mark on solder mask.In addition, work as solder mask and metal (such as copper) rubs mutually When, metal may be scratched, and metal dust may be adhered on solder mask as caused by the metal being scratched.Therefore, easily In the surface appearance defects that solder mask occurs.
In order to improve the surface smoothness of solder mask, hydroquinone epoxy compound should be heated and melted in advance, then passed through The composition of the solder mask composition of hydroquinone epoxy compound comprising fusing is mediated so that hydroquinone epoxy compound is with removing quinhydrones Component outside epoxide is mixed to obtain solder mask composition.However, in such a process, due to hydroquinone epoxy The fusing point of compound is about 138 DEG C to 145 DEG C, it is therefore desirable to for the equipment and time and efforts for heating and melting, causes to hinder The productivity ratio of flux compounds reduces.Further, since hydroquinone epoxy compound has high crystallinity, even if by hydroquinone epoxy Heating causes hydroquinone epoxy compound to be included in molten state in solder mask composition to compound in advance, cools down solder mask composition Hydroquinone epoxy compound may also be caused to crystallize and separate out.Accordingly, it is difficult to using and dry containing fusing quinhydrones oxygen compound Solder mask composition.
Reference listing
Patent document
Patent document 1：JP 2010-266556 A
The content of the invention
The present invention is intended to provide liquid solder mask agent composition, it is although still can be with shape comprising powdered hydroquinone epoxy compound Into glossiness and with the solder mask on the smooth surface of height；Produced with including the solidification comprising the liquid solder mask agent composition The printed substrate of the solder mask of thing.
Included according to the liquid solder mask agent composition of one embodiment of the invention containing carboxy resin (A), thermosetting group Divide (B), photopolymerizable component (C) and Photoepolymerizationinitiater initiater (D).
Heat-curable component (B) includes epoxide (B1).
Epoxide (B1) includes the Powder epoxy compound (B11) represented by following formula (1).
[chemical formula 1]
R in formula (1)1、R2、R3And R4It independently is methyl, hydrogen atom or the tert-butyl group.
Relative to the total amount containing carboxy resin (A), heat-curable component (B) and photopolymerizable component (C), epoxide (B11) amount is 2.0 weight % to 12.0 weight %.
Relative to the carboxyl containing 1 equivalent in carboxy resin (A), the equivalent of epoxide (B1) epoxy group is worked as 1.0 Measure to 4.0 equivalents.
Consolidating comprising the liquid solder mask agent composition is included according to the printed substrate of one embodiment of the invention Change the solder mask of product.
Embodiment
It will now be described for realizing one embodiment of the invention.It should be noted that in description from now on, " (first Base) acryloyl group " mean at least one of " acryloyl group " and " methylacryloyl ".For example, (methyl) acrylate means At least one of acrylate and methacrylate.
It can be used for printing according to the liquid solder mask agent composition (hereinafter referred to as " composition (P) ") of the present embodiment The liquid solder mask agent composition of solder mask is formed on wiring board.
Composition (P) includes triggering containing carboxy resin (A), heat-curable component (B), photopolymerizable component (C) and photopolymerization Agent (D).
Heat-curable component (B) includes epoxide (B1).Epoxide (B1) includes the powder represented by following formula (1) Shape epoxide (B11).Relative to the total amount containing carboxy resin (A), heat-curable component (B) and photopolymerizable component (C), ring The amount of oxygen compound (B11) is 2.0 weight % to 12.0 weight %.Relative to the carboxyl containing 1 equivalent in carboxy resin (A), ring The equivalent of oxygen compound (B1) epoxy group is 1.0 equivalents to 4.0 equivalents.
[chemical formula 2]
R in formula (1)1、R2、R3And R4It independently is methyl, hydrogen atom or the tert-butyl group.
Composition (P) can be applied in substrate, then dried to form coating.Then can be partly sudden and violent by coating Light is exposed to, then carries out developing process, and further heating if desired.Therefore, solder mask can be formed.Even if group Compound (P) includes powdered hydroquinone epoxy compound (B11), and the solder mask can also have the smooth surface of height.
Illustrate the component included in composition (P) in further detail.
(A) containing carboxy resin can be supplied to developability of the coating formed by composition (P) in alkaline solution (i.e., Alkali-developable).
Included containing carboxy resin (A) and contain carboxy resin (A1) (hereinafter also referred to group for example based on acryl-base copolymer Divide (A1)).
Component (A1) can include the compound (hereinafter also referred to component (A11)) with carboxyl but not photopolymerization.Component (A11) polymerization of the unsaturated monomer based on ethene for example including the unsaturated compound based on ethene with carboxyl is included Thing.The unsaturated compound based on ethene with carboxyl can include and be selected from following at least one compound：For example, propylene Acid, methacrylic acid and ω-carboxyl-pla-pcl (n ≈ 2) mono acrylic ester.The unsaturationization based on ethene with carboxyl Compound can also include the compound of dibasic acid anhydride and such as pentaerythritol triacrylate and pentaerythritol acrylate trimethyl Reaction product.Unsaturated monomer based on ethene can also include the unsaturated chemical combination based on ethene without any carboxyl Thing, such as 2- (methyl) acryloyl-oxyethyls phthalic acid ester, 2- (methyl) acryloyl-oxyethyl -2- hydroxyethyls are adjacent (it can be in carbocyclic ring for phthalic acid ester, straight or branched aliphatic (methyl) acrylate and alicyclic (methyl) acrylate In partly contain unsaturated bond).
Component (A1) can also include the compound (A12) with carboxyl and the unsaturated group based on ethene (below Referred to as component (A12)).Component (A12) can be only included containing carboxy resin (A1).
Component (A12) includes such as resin (g), and resin (g) is comprising the unsaturationization based on ethene with epoxy radicals The polymer (g1) of the unsaturated monomer based on ethene of compound (h) and the unsaturated compound based on ethene with carboxyl (g2) intermediate product of the reaction between and the reaction product selected from polybasic carboxylic acid and its at least one compound (g3) of acid anhydrides. Resin (g) is for example, by the epoxy radicals being added to compound (g3) in polymer (g1) and the unsaturated compound based on ethene (g2) obtained in the intermediate product of the reaction between carboxyl in.
Unsaturated compound (h) based on ethene includes compound (h1) such as glycidyl for example with epoxy radicals (methyl) acrylate.Unsaturated compound (h) based on ethene can also include the compound (h2) without any epoxy radicals Such as 2- (methyl) acryloyl-oxyethyl phthalic acid ester.Unsaturated compound (g2) based on ethene preferably comprises acrylic acid At least one of with methacrylic acid.Compound (g3) includes and is selected from following one or more of compounds：It is for example, polynary Carboxylic acid such as phthalic acid, tetrahydrophthalic acid and methyl tetrahydrophthalic acid, and the acid anhydrides of polybasic carboxylic acid.
Component (A12) can also include resin (i), and resin (i) is comprising the unsaturated chemical combination based on ethene with carboxyl The polymer (i1) of the unsaturated monomer based on ethene of thing (j) and the unsaturated compound based on ethene with epoxy radicals (i2) reaction product.Unsaturated monomer based on ethene can also include the unsaturationization based on ethene without any carboxyl Compound.Resin (i) is by making the epoxy radicals in the unsaturated compound (i2) based on ethene and some carboxylics in polymer (i1) Base reacts and obtained.Unsaturated compound (j) based on ethene has included such as acrylic acid, methacrylic acid, ω-carboxyl-poly- The compound of lactone (n ≈ 2) mono acrylic ester, pentaerythritol triacrylate and pentaerythritol acrylate trimethyl.Do not have The unsaturated compound based on ethene for having any carboxyl includes following compound：Such as 2- (methyl) acryloyl-oxyethyl is adjacent Phthalic acid ester, 2- (methyl) acryloyl-oxyethyl -2- hydroxyethyls phthalic acid ester, straight or branched aliphatic (first Base) acrylate and alicyclic (methyl) acrylate (it can partly contain unsaturated bond in carbocyclic ring).Based on ethene Unsaturated compound (i2) preferably comprise glycidyl (methyl) acrylate.
It can also include containing carboxy resin (A2) (hereinafter also referred to " component in addition to component (A1) containing carboxy resin (A) (A2))。
Component (A2) includes such as resin (k), resin (k) be epoxide (k1) with carboxyl based on ethene The intermediate product of reaction between unsaturated compound (k2) and at least one compound selected from polybasic carboxylic acid and its acid anhydrides (k3) reaction product.Resin (k) is for example, by the epoxy radicals and base that are added to compound (k3) in epoxide (k1) Obtained in the intermediate product of the reaction between carboxyl in the unsaturated compound (k2) of ethene.
Epoxide (k1) can include appropriate epoxy resin, such as cresol novolac epoxy and phenol phenol Novolac epoxy resin.Unsaturated compound (k2) based on ethene preferably comprises at least one in acrylic acid and methacrylic acid Kind.Compound (k3) includes and is selected from following at least one compound：For example, polybasic carboxylic acid such as phthalic acid, tetrahydrochysene neighbour's benzene Dioctyl phthalate and methyl tetrahydrophthalic acid, and the acid anhydrides of polybasic carboxylic acid.
Acid number containing carboxy resin (A) is preferably greater than or equal to 20mgKOH/g, more preferably equal to or greater than 30mgKOH/g, Further preferably greater than or equal to 60mgKOH/g.Acid number containing carboxy resin (A) is preferably lower than or equal to 180mgKOH/g, more Preferably lower than or equal to 165mgKOH/g, it is further preferably no larger than or equal to 150mgKOH/g.
Weight average molecular weight containing carboxy resin (A) is preferably 800 to 100000, and more preferably 1000 to 50000.
Pay attention to, weight average molecular weight containing carboxy resin (A) can by by gel permeation chromatography under the following conditions Molecular weight measurement result determines.
GPC devices：The SHODEX SYSTEM 11 manufactured by SHOWA DENKO K.K.,
Post：SHODEX KF-800P, KF-005, KF-003, the KF-001 being connected in series,
Mobile phase：THF,
Flow：1mL/ minutes,
Column temperature：45 DEG C,
Detector：RI,
Conversion：Polystyrene.
Relative to composition (P) solids content, the amount containing carboxy resin (A) is preferably 5 weight % to 85 weight %, more Preferably 10 weight % to 75 weight %, more preferably 15 weight % are to 60 weight %.Pay attention to, the solid of composition (P) Content is defined to be included in the total amount of all components in composition (P) in addition to volatile component (such as solvent).
Heat-curable component (B) can be supplied to composition (P) thermosetting.As described above, heat-curable component (B) includes epoxy Compound (B1), epoxide (B1) include powdered hydroquinone epoxy compound (B11).
Because each molecule of epoxide (B11) only has an aromatic ring, therefore even if by including epoxide (B11) solder mask that composition (P) is formed is decomposed due to heat or light, the also conjugation of far less likely to occur length in solder mask Key.In addition, hydroquinone epoxy compound not nitrogen atom or sulphur atom.Therefore, solder mask is not easy to change.Further, since epoxidation Compound (B11) is difunctionality and contains ehter bond, therefore solder mask has the fragility reduced, improvedd flexibility.Therefore, Crackle caused by the machining as solder mask of solder mask is suppressed.In addition, when heating solder mask, solder mask The fire check as caused by the thermal expansion coefficient difference of substrate and solder mask is suppressed.
In addition, epoxide (B11) has aromatic ring so as to contribute to the heat resistance of improvement solder mask.In addition, epoxidation Up to about 138 DEG C to 145 DEG C of the fusing point of compound (B11).Therefore, when under about 60 DEG C to 80 DEG C of relative low temperature by composition (P) when heating is to form coating, it is not easy to react containing carboxy resin (A) and epoxide (B11).Therefore, containing carboxy resin (A) it is easy to keep unreacted in the coating.Therefore, when making coating develop after light, it can be ensured that high alkali shows Shadow.
Further, since epoxide (B11) has high fusing point, therefore when composition (P) includes epoxide (B11) when, the coating formed by the composition (P) comprising epoxide (B11) has the adherence reduced.
In addition, when (such as at 150 DEG C) heat the coating after development at a proper temperature, the hydrogen in coating Quinone ring oxygen compound (B11) easily softening or fusing, this promotes the thermosetting for being related to hydroquinone epoxy compound (B11) in coating anti- Should.Therefore, the heat resistance of solder mask is improved.
As discussed previously with respect to the total amount containing carboxy resin (A), heat-curable component (B) and photopolymerizable component (C), ring The amount of oxygen compound (B11) is 2.0 weight % to 12.0 weight %.When the amount of epoxide (B11) is more than or equal to 2.0 weights When measuring %, the coating that is formed by composition (P) has a good alkali-developable and low adherence, and by make curing of coatings and The solder mask of formation has good flexibility, hot-cracking resistance and heat resistance.In addition, when relative to containing carboxy resin (A), thermosetting The total amount of component (B) and photopolymerizable component (C), when the amount of epoxide (B11) is less than or equal to 12.0 weight %, welding resistance Layer can have the smooth surface of high glossiness and height.Relative to containing carboxy resin (A), heat-curable component (B) and can light The total amount of polymeric component (C), the amount of epoxide (B11) are more preferably 4.0 weight % to 8.0 weight %.
In addition, relative to the carboxyl containing 1 equivalent in carboxy resin (A), the equivalent of epoxide (B1) epoxy group is 1.0 equivalents to 4.0 equivalents.When the equivalent is more than or equal to 1.0 equivalent, solder mask can have good heat resistance, heat resistanceheat resistant Fragility and cohesive.In addition, when the equivalent is less than or equal to 4.0 equivalent, it is easier to composition (P) is liquefied, and by group The coating that compound is formed has good alkali-developable.Relative to the carboxyl containing 1 equivalent in carboxy resin (A), epoxide (B1) equivalent of epoxy group is more preferably 1.0 equivalents to 3.0 equivalents.When the equivalent is less than or equal to 3.0 equivalent, solder mask There can be optimal crosslink density so that the crack resistance and hot-cracking resistance of solder mask further improve.
Epoxide (B1) can also include the epoxide (B12) in addition to epoxide (B11).
The preferably each molecule of epoxide (B12) has at least two epoxy radicals.Epoxide (B12) can be several Insoluble epoxide, can be general solvable epoxide.
Epoxide (B12) can include and be selected from following at least one component：For example, phenol Novolac epoxy tree Fat (the EPICLON N-775 manufactured by DIC Corporation), cresol novolac epoxy are (by DIC The EPICLON N-695 of Corporation manufactures), bisphenol A epoxide resin is (by Mitsubishi Chemical The jER1001 of Corporation manufactures), bisphenol A-novolac novolac epoxy resins (manufacture by DIC Corporation EPICLON N-865), bisphenol F epoxy resin (by Mitsubishi Chemical Corporation manufacture JER4004P), bisphenol-s epoxy resin (the EPICLON EXA-1514 manufactured by DIC Corporation), bisphenol-A D asphalt mixtures modified by epoxy resin Fat, biphenyl epoxy resin (YX4000 manufactured by Mitsubishi Chemical Corporation), biphenyl novolaks ring Oxygen tree fat (by Nippon Kayaku Co., the NC-3000 of Ltd. manufactures), hydrogenated bisphenol A epoxy resin are (by Nippon The ST-4000D of Steel＆Sumikin Chemical Co., Ltd. manufacture), naphthalene epoxy resins are (by DIC Corporation systems EPICLON HP-4032, EPICLON HP-4700, the EPICLON HP-4770 made), tert-butyl catechol epoxy resin (the EPICLON HP-820 manufactured by DIC Corporation), bicyclopentadiene epoxy resin are (by DIC Corporation The EPICLON HP-7200 of manufacture), adamantane epoxy resin (by Idemitsu Kosan Co., Ltd. manufactures ADAMANTATE X-E-201), Biphenyl Ether epoxy resin is (by Nippon Steel＆Sumikin Chemical Co., Ltd. systems The YSLV-80DE made), special bifunctional epoxy resin (by Mitsubishi Chemical Corporation manufacture YL7175-500 and YL7175-1000；EPICLON TSR-960, the EPICLON TER- manufactured by DIC Corporation 601、EPICLON TSR-250-80BX、EPICLON 1650-75MPX、EPICLON EXA-4850、EPICLON EXA- 4816th, EPICLON EXA-4822 and EPICLON EXA-9726；By Nippon Steel＆Sumikin Chemical Co., Ltd. the YSLV-120TE manufactured) and bisphenol epoxy apart from the above.
Epoxide (B12) can include triglycidyl group isocyanuric acid ester.Triglycidyl group isocyanuric acid ester is special Beta isomer (wherein three epoxy radicals are located at the same side relative to plane s- triazine rings) is not preferably comprised, or to preferably comprise β different Structure body and αisomer (one of epoxy radicals is located at the side different from other two epoxy radicals relative to plane s- triazine rings) Mixture.
Pay attention to, in order to particularly effectively suppress the discoloration of solder mask, and effectively suppress the fragility of solder mask, and provide Flexible to solder mask, epoxide (B12) is preferably free of triglycidyl group isocyanuric acid ester, i.e. composition (P) is preferably not Isocyanuric acid ester containing triglycidyl group.
Epoxide (B12) further preferably includes phosphorous epoxy resin.In this case, the solidification of solder mask composition The anti-flammability of product is improved.The example of phosphorous epoxy resin may include the bisphenol F epoxy resin of phosphoric acid modification (by DIC EPICLON EXA-9726 and the EPICLON EXA-9710 of Corporation manufactures) and by Nippon Steel＆Sumikin The Epotohto FX-305 of Chemical Co., Ltd. manufactures.
Epoxide (B12) preferably comprises the compound of fusing point or softening point greater than or equal to 60 DEG C.In such case Under, the adherence of the coating formed by composition (P) reduces.The fusing point or softening point of the compound are more preferably 60 DEG C to 160 ℃。
In addition, epoxide (B12) preferably comprises no aromatic compound.In this case, the resistance to thermal change of solder mask Color improves.Further preferably epoxide (B12) include fusing point or softening point greater than or equal to 60 DEG C without aromatic compound.
Especially, epoxide (B12) preferably comprises has two with annular aliphatic structure and each molecule Or more epoxy radicals alicyclic epoxide compound (B121).In this case, the resistance to thermochromism of solder mask especially changes It is kind.
In addition, the fusing point or softening point of alicyclic epoxide compound (B121) are preferably greater than or equal to 60 DEG C.Aliphatic ring Oxygen compound (B121) does not have any aromatic ring further preferably.Particularly preferred alicyclic epoxide compound (B121), which has, to be higher than or waits In 60 DEG C of fusing points or softening point and do not have any aromatic ring.
The example of alicyclic epoxide compound (B121) can include the 1,2- rings of double (the hydroxymethyl)-n-butyl alcohols of 2,2- Oxygen -4- (2- Oxyranyles) hexamethylene adduct is (for example, the EHPE3150 manufactured by DAICEL CORPORATION, softening Point be 70 DEG C to 90 DEG C), 3,4- epoxycyclohexyl-methyl -3', 4'- epoxycyclohexane carboxylates are (for example, by DAICEL The CELLOXIDE 2021P of CORPORATION manufactures), (3,3', 4,4'- diepoxy) dicyclohexyl is (for example, by DAICEL CORPORATION manufacture CELLOXIDE 8000), 6-caprolactone be modified 3', 4'- epoxycyclohexyl-methyl 3,4- epoxide rings Cyclohexane carboxylic-acid ester (for example, the CELLOXIDE 2081 manufactured by DAICEL CORPORATION), (3, the 4- rings of BTCA four Oxygen cyclohexyl methyl) modified 6-caprolactone (for example, the EPOLEAD GT401 manufactured by DAICEL CORPORATION), hydrogen Change bisphenol A epoxide resin (for example, by NIPPON STEEL＆SUMIKIN CHEMICAL CO., the ST-3000 of LTD. manufactures, by The ST-4000D (softening point is 85 DEG C to 100 DEG C) of NIPPON STEEL＆SUMIKIN CHEMICAL CO., LTD. manufacture, by Mitsubishi Chemical Corporation manufacture YX8000 and by Mitsubishi Chemical The YX-8034 of Corporation manufactures) and A Hydrogenated Bisphenol A F epoxy resin.
Heat-curable component (B) can only include epoxide (B1)；However, heat-curable component (B) can also include division ring The compound of such as thermosetting monomer and thermoset prepolymer outside oxygen compound (B1).For example, heat-curable component (B) can wrap Containing selected from following at least one compound：Polyimide resin, polyamide-imide resin, cyanate resin, phenolic resin, honey Polyimide resin, urea resin, silicones, polyester resin, cyanate ester resin and its modified resin.
Photopolymerizable component (C) includes monomer (C1) for example with the unsaturated group based on ethene and with being based on second At least one of prepolymer (C2) of the unsaturated group of alkene.Pay attention to, the component in containing carboxy resin (A) excludes Outside photopolymerizable component (C).
Monomer (C1) can include and be selected from following at least one compound：For example, simple function (methyl) acrylate, such as 2- Hydroxyethyl (methyl) acrylate；And multifunctional (methyl) acrylate, such as diethylene glycol two (methyl) acrylate, three Hydroxymethyl-propane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) propylene Acid esters, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) third The acrylate of pentaerythrite six and Tricyclodecane Dimethanol two (methyl) acrylate that olefin(e) acid ester, 6-caprolactone are modified.
Photopolymerizable component (C), which can include each molecule, has the trifunctional compound of three unsaturated bonds.Trifunctional Compound can include and be selected from following at least one compound：For example, what trimethylolpropane tris (methyl) acrylate, EO were modified Trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, (first of ethoxylation isocyanuric acid three Base) acrylate, 6-caprolactone be modified three-(2- acryloyl-oxyethyls) isocyanuric acid ester and the (first of ethoxylated glycerol three Base) acrylate.
Monomer (C1) may include phosphorus-containing compound (phosphorous unsaturated compound).In this case, composition (P) consolidates Changing the anti-flammability of product is improved.Phosphorous unsaturated compound can include and be selected from following at least one compound：For example, 2- Methacryloxyethyl phosphate ester acid is (for example, the light ester P-1M manufactured by Kyoeisha Chemical Co., Ltd.s With light ester P-2M), 2- acryloyl-oxyethyls phosphate ester acid (for example, by Kyoeisha Chemical Co., Ltd.s manufacture Light acrylate P-1A), xenyl -2- methacryloxyethyls phosphate is (for example, by Daihachi Chemical Industry Co., Ltd.s manufacture MR-260) and by Showa Highpolymer K.K. manufacture HFA series (for example, HFA-6003 and HFA-6007, its be dipentaerythritol acrylate with HCA (miscellaneous -10- phospho hetero phenanthrenes of 9,10- dihydro-9-oxies - 10- oxides) addition reaction product, and HFA-3003 and HFA-6127, it is the dipentaerythritol of caprolactone modification Six acrylate and the product of HCA (miscellaneous -10- phospho hetero phenanthrenes -10- oxides of 9,10- dihydro-9-oxies) addition reaction).
Prepolymer (C2) can include following at least one：For example, by the way that the unsaturated group based on ethene is added to The prepolymer obtained in polymerized monomer with the unsaturated bond based on ethene；With based on oligomeric (methyl) acrylate prepolymer The compound of thing.Compound based on oligomeric (methyl) acrylic ester prepolymer can include and be selected from following at least one chemical combination Thing：For example, epoxy (methyl) acrylate, polyester (methyl) acrylate, carbamate (methyl) acrylate, alkyd tree Fat (methyl) acrylate, organic siliconresin (methyl) acrylate and spirane resin (methyl) acrylate.
Relative to the amount containing carboxy resin (A), the amount of photopolymerizable component (C) is preferably 1 weight % to 50 weight %, more Preferably 10 weight % to 45 weight %, more preferably 21 weight % are to 40 weight %.
Photoepolymerizationinitiater initiater (D) can include known material.For example, Photoepolymerizationinitiater initiater (D) can be included selected from following One or more of compounds：For example, benzoin and its alkyl ether；Compound based on acetophenone, such as acetophenone and benzyl two Methyl ketal；Compound based on anthraquinone, such as 2-methylanthraquinone；Compound based on thioxanthones, such as 2,4- dimethyl thioxanthones, 2,4- diethyl thioxanthones, ITX, ITX and 2,4- diisopropylthioxanthones；Based on hexichol first The compound of ketone, such as benzophenone and 4- benzoyl -4'- methyldiphenyl thioethers；Compound based on xanthone, such as 2,4- bis- Isopropyl xanthone；The compound of nitrogen atom, such as 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholino -1- acetone；Base In the compound of Alpha-hydroxy alkyl phenones, such as 1- hydroxy-cyclohexyl-phenyls -one, 2- hydroxy-2-methyls -1- phenyl -propyl- 1- Ketone, 1- [4- (2- hydroxyl-oxethyls)-phenyl] -2- hydroxy-2-methyl -1- propyl- 1- ketone, 2- hydroxyls -1- 4- [4- (2- hydroxyls - 2- methyl-propanoyls)-benzyl] phenyl } -2- methyl -propyl- 1- ketone and phenylglyoxalates methyl esters；Based on alpha-aminoalkyl benzophenone Compound, such as 2- methyl isophthalic acids-(4- methylphenyl-sulfanyls) -2- morpholino propyl- 1- ketone, 2- benzyl -2- dimethylamino -1- (4- Quinoline is for phenyl)-butanone -1 and 2- (dimethylamino) -2- [(4- aminomethyl phenyls) methyl] -1- [4- (4- morpholinyls) phenyl] -1- Butanone；Photoepolymerizationinitiater initiater based on monoacylphosphine oxides, such as 2,4,6- trimethylbenzoy-diphenies-phosphine oxide and 2, 4,6- trimethylbenzoyls-Ethyl-phenyl-phosphinate；Photoepolymerizationinitiater initiater based on acylphosphanes, such as double-(2,4,6- tri- Methyl benzoyl) phenyl phosphine oxide, double-(2,6- dichloro-benzoyls base) phenyl phosphine oxide, double-(2,6- dichloro-benzoyls Base) -2,5- 3,5-dimethylphenyls phosphine oxide, double-(2,6- dichloro-benzoyls base) -4- propylphenylphosphine oxides, double-(2,6- dichloros Benzoyl) -1- naphthyls phosphine oxide, double-(2,6- Dimethoxybenzoyls) phenyl phosphine oxide, double-(2,6- dimethoxy benzenes Formoxyl) -2,4,4- trimethylpentylphosphine oxides, double-(2,6- Dimethoxybenzoyls) -2,5- 3,5-dimethylphenyl phosphine oxides (2,5,6- trimethylbenzoyls) -2,4,4- trimethylpentylphosphine oxides；And the Photoepolymerizationinitiater initiater based on oxime ester, such as 1,2- octanediones, 1- [4- (thiophenyl) -, 2- (O- benzoyls oxime)] and ethyl ketone, 1- [9- ethyls -6- (2- toluyls Base) -9H- carbazole -3- bases] -, 1- (O- acetyl oxime).
Photoepolymerizationinitiater initiater (D) preferably comprises Photoepolymerizationinitiater initiater based on double acylphosphine oxides and based on Alpha-hydroxy alkyl The Photoepolymerizationinitiater initiater of benzophenone.In this case, can be from its surface when exposed to light by the coating that composition (P) is formed It is fully cured to its deep.Photoepolymerizationinitiater initiater (D) include Photoepolymerizationinitiater initiater based on double acylphosphine oxides and based on α- The Photoepolymerizationinitiater initiater of hydroxyalkylphenones and without in the case of the Photoepolymerizationinitiater initiater based on monoacylphosphine oxides, sudden and violent It is exposed under light, curability of the coating in its deep becomes especially high.Relative to Photoepolymerizationinitiater initiater (D) amount, based on double acyls The total amount of the Photoepolymerizationinitiater initiater of base phosphine oxide and Photoepolymerizationinitiater initiater based on Alpha-hydroxy alkyl phenones be preferably 5 weight % extremely 100 weight %, more preferably 7 weight % are to 100 weight %, more preferably 9 weight % to 100 weight %, particularly preferably For 70 weight % to 100 weight %.Relative to the Photoepolymerizationinitiater initiater based on double acylphosphine oxides and based on Alpha-hydroxy alkylbenzene The total amount of the Photoepolymerizationinitiater initiater of ketone, the amount of the Photoepolymerizationinitiater initiater based on double acylphosphine oxides is preferably 1 weight % to 99 weights Measure %, more preferably 5 weight % to 60 weight %, more preferably 10 weight % to 40 weight %.
Photoepolymerizationinitiater initiater (D) is further preferably comprising the Photoepolymerizationinitiater initiater based on acylphosphine oxide and based on acetaldehyde acid phenenyl ester Photoepolymerizationinitiater initiater.In this case, can be easily from its table when exposed to light by the coating that composition (P) is formed Face is fully cured to its deep.Relative to Photoepolymerizationinitiater initiater (D) amount, Photoepolymerizationinitiater initiater and base based on acylphosphine oxide In the total amount of the Photoepolymerizationinitiater initiater of acetaldehyde acid phenenyl ester be preferably 3 weight % to 100 weight %, more preferably 6 weight % to 100 Weight %, more preferably 9 weight % are to 100 weight %, particularly preferably 50 weight % to 100 weight %.Relative to base In the total amount of the Photoepolymerizationinitiater initiater of acylphosphine oxide and Photoepolymerizationinitiater initiater based on acetaldehyde acid phenenyl ester, based on acylphosphine oxide The amount of Photoepolymerizationinitiater initiater be preferably 1 weight % to 99 weight %, more preferably 5 weight % to 60 weight %, it is further excellent 10 weight % are elected as to 40 weight %.
Relative to the amount containing carboxy resin (A), the amount of Photoepolymerizationinitiater initiater (D) is preferably 0.1 weight % to 30 weight %, More preferably 1 weight % to 25 weight %.
Composition (P) can also include known photopolymerization promoter and known sensitizer.For example, composition (P) can wrap Containing selected from following at least one compound：Benzoin and its alkyl ether；Compound based on acetophenone, such as acetophenone and benzyl Dimethyl ketal；Compound based on anthraquinone, such as 2-methylanthraquinone；Compound based on thioxanthones, such as 2,4- dimethyl thioxanthenes Ketone, 2,4- diethyl thioxanthones, ITX, ITX and 2,4- diisopropylthioxanthones；Based on two The compound of Benzophenone, such as benzophenone and 4- benzoyl -4'- methyldiphenyl thioethers；Compound based on xanthone, such as 2, 4- diisopropyl xanthones；Compound based on alpha-alcohol ketone, such as 2- hydroxy-2-methyls -1- phenyl -propyl- 1- ketone；Nitrogen atom Compound, such as 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholino -1- acetone.In addition to Photoepolymerizationinitiater initiater (D), combination Thing (P) can also include the known photopolymerization promoter based on tertiary amine and the known sensitizer based on tertiary amine such as to dimethyl benzene Ethyl formate, ESCAROL 507 isopentyl ester and 2- dimethyl aminoethyl benzoic ethers.If desired, combine Thing (P) can include and be selected from following at least one Photoepolymerizationinitiater initiater：For visible light exposure Photoepolymerizationinitiater initiater and be used for The Photoepolymerizationinitiater initiater of near infrared light exposure.In addition to Photoepolymerizationinitiater initiater (D), composition (P) can include such as following change Compound：Coumarin derivative, such as 7- diethylamino -4- methylcoumarins, it is the sensitizer for laser explosure；Carbocyanine Dyestuff；And xanthene dye.
Composition (P) can include Chinese white.In this case, the solder mask formed by composition (P) is colored For white, therefore solder mask can obtain high light reflectivity.Thus, it is possible to obtain light reflects solder mask.Light-emitting component (such as Light emitting diode) it can be appropriately mounted on the printed substrate including light reflection solder mask.Especially, composition (P) is excellent Choosing is used as Chinese white comprising titanium dioxide (E).In this case, solder mask can obtain extra high light reflectivity.
Titanium dioxide (E) can include at least one of rutile titanium dioxide and anatase titanium dioxide.Especially Ground, titanium dioxide (E) preferably comprise the rutile titanium dioxide with low catalytic activity and high thermal stability.Rutile-type two Titanium oxide is industrially manufactured by chlorine method or sulfuric acid process.In the present embodiment, rutile titanium dioxide can include logical Cross the rutile titanium dioxide of chlorine method manufacture and at least one of the rutile titanium dioxide manufactured by sulfuric acid process.
Relative to 100 mass parts (A) containing carboxy resin, the amount of titanium dioxide (E) is preferably 15 mass parts to 500 mass Part.Relative to the total amount containing carboxy resin (A), heat-curable component (B) and photopolymerizable component (C), the amount of titanium dioxide (E) is excellent Elect 3 weight % to 220 weight %, more preferably 10 weight % to 180 weight % as.
Composition (P) can include component (F), and component (F) includes at least one of melamine and melamine derivative.This In the case of, the cohesive increase between the cured product and metal (such as copper) of composition (P).Therefore, composition (P) is especially suitable Cooperate as the insulating materials for printed substrate.In addition, the resistance to plating of the cured product of composition (P), i.e. chemical plating ni au Whitening resistance (whitening resistance) during processing is improved.
Melamine is 2,4,6- triamido -1,3,5- triazines and is commercially available.Melamine derivative is preferably each molecule tool There is the compound of triazine ring and amino.The example of melamine derivative may include：Guanamines；Acetylguanamine；Benzoguanamine；S- triazines are spread out Biology, such as 2,4- diaminourea -6- methacryloxyethyl-S- triazines, 2- vinyl -4,6- diaminourea-S- triazines, 2- second Alkenyl -4,6- diaminourea-S- triazines/isocyanuric acid adduct and 2,4- diaminourea -6- methacryloxyethyls-S- three Piperazine/isocyanuric acid adduct；And the reaction product between melamine and acid anhydrides, such as melamine-tetrahydrophthalic acid ester.Melamine spreads out The more specific examples of biology may include VD-1, VD-2 and the VD-3 manufactured by SHIKOKU CHEMICALS CORPORATION.
When composition (P) includes component (F), relative to the amount containing carboxy resin (A), the amount of component (F) is preferably 0.1 Weight % to 10 weight %, more preferably 0.5 weight % are to 5 weight %.
Composition (P) can include organic solvent.Organic solvent is used to make composition (P) liquefy or be formed with composition (P) Varnish, and adjust viscosity, applicability and film forming.
Organic solvent can include and be selected from following at least one compound：For example, straight chain, side chain, secondary alcohol or polyalcohol, such as Ethanol, propyl alcohol, isopropanol, hexanol and ethylene glycol；Compound based on ketone, such as methyl ethyl ketone and cyclohexanone；Aromatic hydrocarbons, such as toluene And dimethylbenzene；Petroleum aromatic mixed solvent, as Swazol series (is manufactured) by Maruzen Petrochemical Co., Ltd.s (manufactured with Solvesso series by Exxon Mobil Chemical Corporation)；Compound based on cellosolve, such as Cellosolve and butyl cellosolve；Compound based on carbitol, such as carbitol and butyl carbitol；Based on propylene glycol alkyl ether Compound, such as propylene glycol monomethyl ether；Compound based on polypropylene glycol alkyl ether, such as dipropylene glycol methyl ether；Based on acetic acid esters Compound, such as ethyl acetate, butyl acetate, cellosolve acetate and carbitol acetate；And based on dialkyl group glycol ethers Compound.
The amount of each component in appropriate regulation composition (P) causes composition (P) to have photocurable and can use alkali Property solution development.
In the case where composition (P) includes organic solvent, the amount for preferably adjusting organic solvent drying by combining During the coating that thing (P) is formed, organic solvent is volatilized rapidly, i.e., organic solvent is not kept in dry coating.Especially, relatively In whole composition (P), the amount of organic solvent be preferably 0 weight % to 99.5 weight %, more preferably 15 weight % extremely 60 weight %.Pay attention to, because the appropriate amount of organic solvent depends on painting method, therefore the amount of organic solvent is preferably according to coating Method is suitably adjusted.
Composition (P) can also include component apart from the above, as long as not damaging the effect of the present embodiment.
For example, composition (P) can include antioxidant.Antioxidant contributes to solder mask consolidating from its surface to its deep Change, and additionally aid the improvement of the cohesive of solder mask and the improvement of resistance to thermochromism.
The fusing point of antioxidant is preferably 50 DEG C to 150 DEG C.In such a case, it is possible to prevent antioxidant from by welding resistance Oozed out in the coating that agent composition is formed.In addition, prevent the crystal of antioxidant from separating out.Therefore, the surface smoothness of solder mask Improved.
Antioxidant can include and be selected from following at least one compound：For example, the antioxidant based on hindered phenol, such as： The IRGANOX 245 (fusing point is 76 DEG C to 79 DEG C) that is manufactured by BASF Corporation, (fusing point is 104 DEG C to IRGANOX 259 To 108 DEG C), IRGANOX 1035 (fusing point is 63 DEG C to 67 DEG C), IRGANOX 1098 (fusing point is 156 DEG C to 161 DEG C), IRGANOX1010 (fusing point is 110 DEG C to 125 DEG C), IRGANOX 1076 (fusing point is 50 DEG C to 55 DEG C) and IRGANOX 1330 (fusing point is 240 DEG C to 245 DEG C)；Manufactured by ADEKA CORPORATION ADEKA STAB AO-20 (fusing point be 220 DEG C extremely 222 DEG C), ADEKA STAB AO-30 (fusing point is 183 DEG C to 185 DEG C), (fusing point is 210 DEG C to 214 to ADEKA STAB AO-40 DEG C), ADEKA STAB AO-50 (fusing point is 51 DEG C to 54 DEG C), ADEKA STAB AO-60 (fusing point is 110 DEG C to 130 DEG C), ADEKA STAB AO-80 (fusing point is 110 DEG C to 120 DEG C) and ADEKA STAB AO-330 (fusing point is 243 DEG C to 245 DEG C)； By SHIPRO KASEI KAISHA, the SEENOX224M (fusing point is 129 DEG C to 132 DEG C) and SEENOX326M of Ltd. manufactures are (molten Point is 241 DEG C to 249 DEG C)；By Sumitomo Chemical CO., (fusing point is higher than the SUMILIZER GA-80 of Ltd. manufactures Or equal to 110 DEG C) and SUMILIZER MDP-S (fusing point is greater than or equal to 128 DEG C)；And by Kawaguchi Chemical The Antage BHT (fusing point is greater than or equal to 69 DEG C) of Industry Co., LTD manufacture, Antage W-300 (fusing point be higher than or Equal to 205 DEG C), (fusing point is greater than or equal to 120 by Antage W-400 (fusing point be greater than or equal to 120 DEG C) and Antage W-500 ℃).Especially, antioxidant preferably comprises IRGANOX1010 (fusing point is 110 DEG C to 125 DEG C).
Composition (P) can also include the inorganic filler in addition to Chinese white.In such a case, it is possible to reduce by group The shrinkage factor of the film that compound (P) is formed during curing.Inorganic filler can include and be selected from following at least one compound：Example Such as, barium sulfate, crystalline silica, nano silicon, CNT, talcum, bentonite, aluminium hydroxide and magnesium hydroxide. Relative to the amount containing carboxy resin (A), the total amount of Chinese white and inorganic filler is such as 0 weight % to 300 weight %.
Composition (P) can include and be selected from following at least one resin：With end-blockings such as caprolactam, oxime, maleates Inferior cresyl vulcabond, morpholine diisocyanate, the envelope of isophorone diisocyanate and hexamethylene diisocyanate It is isocyanate terminated；By the way that (methyl) acrylic acid is added into epoxy resin (such as bisphenol A epoxide resin, phenol novolacs ring Oxygen tree fat, cresol novolac epoxy and cycloaliphatic epoxy resin) and the resin of acquisition；And polymer compound (example Such as diallyl phthalate resin, phenoxy resin, carbamate resins and fluorine resin).
Composition (P) can include curing agent so that epoxide (B1) solidifies.Curing agent can include selected from it is following extremely A kind of few compound：For example, imdazole derivatives, as imidazoles, 2-methylimidazole, 2- ethyl imidazol(e)s, 2-ethyl-4-methylimidazole, 2- phenylimidazoles, 4- phenylimidazoles, 1- cyano ethyl -2- phenylimidazoles and 1- (2- cyano ethyls) -2- ethyl -4- methyl miaows Azoles；Amines, such as dicyandiamide, benzyldimethylamine, 2,4,4- (dimethylamino)-N, N- dimethyl benzyl amine, 4- methoxyl group-N, N- dimethyl benzyl amines and 4- methyl-N, N- dimethyl benzyl amine；Hydrazide compound, such as adipic acid hydrazides and decanedioic acid hydrazides； Phosphorus compound, such as triphenylphosphine；Acid anhydrides；Phenol；Mercaptan；Lewis acid amine complex；AndSalt.The commercially available production of above-claimed cpd The example of product can include 2MZ-A, 2MZ-OK, 2PHZ, the 2P4BHZ manufactured by Shikoku Chemicals Corporation With 2P4MHZ (name of product of the commercially available prod of the compound based on imidazoles), the U- manufactured by San-Apro Ltd. CAT3503N and U-CAT3502T (name of product of the commercially available prod of the blocked isocyanate of dimethyl amine), and by San- DBU, DBN, U-CATSA102 and U-CAT5002 (bicyclic amidine compound and its salt) of Apro Ltd. manufactures.
Composition (P) can also include the cohesive imparting agent in addition to component (F).The example of cohesive imparting agent can wrap Include guanamines, acetylguanamine, benzoguanamine, and S- pyrrolotriazine derivatives such as 2,4- diaminourea -6- methacryloxyethyls-S- Triazine, 2- vinyl -4,6- diaminourea-S- triazines, 2- vinyl -4,6- diaminourea-S- triazines/isocyanuric acid adduct and 2,4- diaminourea -6- methacryloxyethyls-S- triazines/isocyanuric acid adduct.
Composition (P) can include and be selected from following at least one compound：Curing accelerator；Colouring agent；Such as organosilicon With the copolymer of acrylate；Levelling agent；Cohesive imparting agent such as silane coupler；Thixotropic agent；Polymerization inhibitor；Anti-clouding agent；It is fire-retardant Agent；Defoamer；Antioxidant；Surfactant；And polymeric dispersant.
The amount of amines in composition (P) is preferably as small as possible.In this case, consolidating comprising composition (P) The electrical insulation characteristics for changing the layer of product are less likely to be damaged.Especially, relative to the amount containing carboxy resin (A), amines Amount is preferably less than or equal to 6 weight %, further preferably less than or equal to 4 weight %.
The composition as described above of composition (P) uses such as three rollers, ball mill or sand mill by known kneading method It is combined and mediates obtains composition (P).When the composition of composition (P) is included as liquid or has the component of low viscosity When, can first using except as liquid or with low viscosity component in addition to composition mediate, then can will be used as liquid or Component with low viscosity is added in the mixture through kneading to obtain composition (P).
On storage stability, some compositions of composition (P) can be mixed to obtain the first mixture, can be by it Remaining composition is mixed to obtain the second mixture.That is, composition (P) can include the first mixture and the second mixture.For example, can With in advance that the photopolymerizable component (C) in composition (P) all the components, some organic solvents and heat-curable component (B) is mixed Merge and disperse to obtain the first mixture, remaining composition of composition (P) can be mixed and disperseed to obtain the second mixture. In such a case, it is possible to the desired amount of first mixture and the second mixture are mixed to obtain for forming the mixed of solder mask Compound.
Illustrate the example for being used to obtain the method for the printed substrate for the solder mask for including being formed by composition (P).
First, core material is prepared.Core material includes for example, at least an insulating barrier and at least one conducting wiring.Thereon Coating is formed by composition (P) on the surface of core material formed with conducting wiring.Method for forming coating is for example to apply Use method.In application process, for example, composition (P) is applied in core material to form wet coating.For using composition (P) application process is selected from following known method：For example, infusion process, spraying process, spin-coating method, rolling method, curtain coating method and screen printing Brush method.Then, in order that the organic solvent in composition (P) volatilizees, wet coating is done at a temperature of such as 60 DEG C to 120 DEG C It is dry to obtain coating.
It is partially cured to carry out to expose the coat to light.In order to exposed to light, for example, negative mask is placed on into coating On, then irradiate coating with ultraviolet.The expose portion of negative mask including transmitting UV and not transmitting UV it is not sudden and violent Reveal part.For example, it is used as negative mask using optical tool such as mask film and drying plate.The light source of ultraviolet is selected from：It is for example, chemical Lamp, low pressure mercury lamp, medium pressure mercury lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, xenon lamp and metal halide lamp.Pay attention to, can use to remove makes With the exposure method outside the method for negative mask.For example, light can be exposed the coat to by direct patterning method, wherein Ultraviolet from light source is only irradiated to the part for needing to be exposed to light of coating.Light source for direct patterning method selects From：For example, high-pressure sodium lamp；Ultrahigh pressure mercury lamp；Metal halide lamp；G- lines (wavelength 436nm)；H- lines (wavelength 405nm)；I- lines (wavelength 365nm)；And g- lines, h- lines and i- lines both or more person combination.
Then, coating experience developing process is made to remove the unexposed portion of removing coating., can be according to group in developing process The composition of compound (P) uses appropriate developer.Developer is：For example, comprising alkali metal salt and alkali metal hydroxide extremely A kind of few alkaline aqueous solution；Or organic amine.More specifically, alkaline aqueous solution, which includes, is selected from following at least one compound： For example, sodium carbonate, potassium carbonate, ammonium carbonate, sodium acid carbonate, saleratus, ammonium hydrogen carbonate, sodium hydroxide, potassium hydroxide, hydroxide Ammonium, tetramethyl ammonium hydroxide and lithium hydroxide.The solvent of alkaline aqueous solution can be individually for water, or water and hydrophilic organic solvent The mixture of (such as lower alcohol).Organic amine includes and is selected from following at least one compound：For example, MEA, diethanol Amine, triethanolamine, monoisopropanolamine, diisopropanolamine (DIPA) and triisopropanolamine.
Then, the curing of coatings after developing process is made by heating.Such as under 120 DEG C to 200 DEG C of heating-up temperature Coating is heated 30 minutes to 120 minutes.By heating the intensity for making curing of coatings improve solder mask, hard under these conditions Degree and chemical resistance.If desired, can before heating, heating after or heating before and after further irradiated with ultraviolet Coating.In this case, the photocuring of coating is further carried out.
By method as described above, the solder mask of the cured product comprising composition (P) is formd in core material.Cause This, obtains the printed substrate including solder mask.
As described above, in the present embodiment, although composition (P) includes powdered hydroquinone epoxy compound (B11), by The solder mask that composition (P) is formed can also have the smooth surface of height.Accordingly it is also possible to by including above-mentioned administration side The glossiness more than or equal to 50 is realized on the surface for the solder mask that the method for method is formed.Glossiness on the surface of solder mask is big In or equal in the case of 50, the smoothness on the surface of solder mask is very high.Therefore, especially prevent from producing cunning on solder mask Trace, and especially prevent when metal dust caused by solder mask and metal (such as copper) phase mutual friction is adhered on solder mask, So that the less generation of the surface appearance defects of solder mask.
Embodiment
1. the preparation of the solution containing carboxy resin
(1) solution A containing carboxy resin
By 80 mass parts methacrylic acids, 80 mass parts methyl methacrylates, 20 mass parts styrene, 20 mass parts first Base n-butyl acrylate, 360 mass parts dipropylene glycol monomethyl ethers and 5 mass parts azobis isobutyronitriles are added to equipped with returned cold Condenser, thermometer, nitrogen displacement glass tube and agitator four-neck flask in.Under nitrogen flowing, by four-neck flask at 75 DEG C In mixture heat 5 hours to carry out polymerisation, obtain 36% copolymer solution.By 0.1 mass parts quinhydrones, 64 mass parts Glycidyl methacrylate and 0.8 mass parts dimethyl benzyl amine are added in copolymer solution, then at 80 DEG C Mixture is heated 24 hours to carry out addition reaction.As a result, the change with carboxyl and the unsaturated group based on ethene is obtained 42 weight % solution of compound.The acid number of the solid constituent of the solution is 105mgKOH/g.Tree containing carboxyl is used as using the solution Lipoprotein solution A.
(2) solution B containing carboxy resin
The modified epoxy acrylic ester solution of preparation acid (manufactured by SHOWA DENKO K.K., Ripoxy PR-300CP, Concentration is 65%, and the acid number of solid constituent is 78mgKOH/g) it is used as solution B containing carboxy resin.
2. the preparation of embodiment 1 to 17 and comparative example 1 to 10
The component listed by mixing table 1 below into 4 " composition " is mediated to obtain and the mixture obtained using three rollers Obtain the solder mask composition of embodiment 1 to 17 and comparative example 1 to 10.Pay attention to, the detailed description for the component listed in table is as follows.
* Photoepolymerizationinitiater initiater (IRGACURE 907)：2- methyl isophthalic acids-(4- methylphenyl-sulfanyls) -2- morpholino propyl- 1- ketone, Manufactured by BASF, article number IRGACURE 907.
* Photoepolymerizationinitiater initiater (DETX)：2,4- diethyl thioxanthene-9-ones.
* Photoepolymerizationinitiater initiater (IRGACURE 819)：Double (2,4,6- trimethylbenzoyl)-phenyl phosphine oxides, by BASF is manufactured, article number IRGACURE 819.
* Photoepolymerizationinitiater initiater (IRGACURE 1173)：2- hydroxy-2-methyls -1- phenyl -propyl- 1- ketone, is manufactured by BASF, Article number IRGACURE 1173.
* Photoepolymerizationinitiater initiater (IRGACURE 184)：1- hydroxy-cyclohexyl-phenyl -one, is manufactured, article number by BASF IRGACURE 184。
* Photoepolymerizationinitiater initiater (IRGACURE TPO)：2,4,6- trimethylbenzoy-diphenies-phosphine oxide, by BASF Manufacture, article number IRGACURE TPO.
* Photoepolymerizationinitiater initiater (IRGACURE 379)：2- dimethylaminos -2- (4- Methyl-benzvls) -1- (4- morpholines -4- Base-phenyl)-butyl- 1- ketone, manufactured by BASF, article number IRGACURE 379.
* titanium dioxide：The rutile titanium dioxide manufactured by chlorine method, by ISHIHARA SANGYO KAISHA, LTD. manufacture, article number CR-90.
* barium sulfate：Manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD., article number BARIACE B31.
* colouring agent：Manufactured by BASF, article number Heliogen Green K8730.
* epoxide YDC-1312：Powdered hydroquinone epoxy compound (the 2,5- di-t-butyl hydrogen represented by formula (1) Quinone diglycidyl ether), manufactured by Nippon Steel＆Sumikin Chemical Co., Ltd.s, article number YDC-1312.
* epoxide EPICLON N-665 75% solution：Cresol novolac epoxy, by DIC Corporation is manufactured, trade name EPICLON N-665.
* epoxide EHPE3150 75% solution：1,2- epoxy -4- (the 2- of double (the hydroxymethyl)-n-butyl alcohols of 2,2- Oxyranyle) hexamethylene adduct, manufactured by Daicel Corporation, article number EHPE3150, softening point is 70 DEG C To 90 DEG C.
* epoxide TEPIC-SP：Triglycidyl group isocyanuric acid ester, by NISSAN CHEMICAL INDUSTRIES, Ltd. are manufactured, article number TEPIC-SP.
* organic solvent：Metering system diethylene glycol (DEG), manufactured by Nippon Nyukazai Co., Ltd.s, article number MFDG.
* photopolymerizable monomer DPHA：Dipentaerythritol acrylate, manufactured by Nippon Kayaku Co., Ltd.s, Article number KAYARAD DPHA.
* defoamer：Manufactured by Shin-Etsu Chemical Co., Ltd.s, article number KS-66.
3. evaluation test
(1) preparation of test sample
Prepare the glass epoxide copper-clad laminate for including the copper foil that thickness is 35 μm.By in glass epoxide copper-clad laminate On be etched to form conducting wiring to obtain core material.The surface of the core material of acquisition is all coated by silk screen print method There is solder mask composition, then be dried to obtain the coating that thickness is 20 μm by heating 20 minutes at 80 DEG C.Will Negative mask is directly placed on coating, is covered using the exposure device equipped with metal halide lamp with ultraviolet irradiation negative-appearing image Mould, thus with 450mJ/cm2Light exposure coating is selectively exposed to light.Then, negative mask is removed from coating, and Coating is set to develop with aqueous sodium carbonate so that the part solidified by exposure to light of coating is retained as printed substrate On solder mask.Solder mask is further heated 60 minutes at 150 DEG C and makes its heat cure.As a result, obtaining includes solder mask Test sample.
Following evaluation test is carried out to each test sample.
(2) evaluation of low adherence
When preparing each test sample, when removing negative mask from coating after light, coating is observed The situation of the coating after stripper-resistance and removal negative mask between negative mask.Evaluation of result is as follows.
A：Viscosity is not observed when touching the coating before being exposed to light with finger, and is being removed after light The vestige of negative mask is not observed after negative mask on coating.
B：Slight viscosity is observed when touching the coating before being exposed to light with finger, and is being moved after light Except the vestige for observing negative mask after negative mask on coating.
C：Obvious viscosity is observed when touching the coating before being exposed to light with finger, and is being moved after light After negative mask, coating is damaged.
(3) photosensitive evaluation (remaining section)
By for the test mask of exposure (the stage exposure meter manufactured by Hitachi Chemical Co., Ltd. 21 sections of PHOTEC) directly place and be adhered to by low pressure on the coating formed in each embodiment and comparative example.So Afterwards, using the two-sided exposure of low pressure adhesion type equipped with metal halide lamp manufactured by ORC Manufacturing Co., Ltd.s Electro-optical device (model ORC HMW680GW) is by testing mask with 450mJ/cm2Irradiation energy density with ultraviolet irradiate apply Layer.Then coating is made to develop with developer (concentration is 1 weight % aqueous sodium carbonate).Coating is evaluated according to remaining hop count Photonasty.
(4) evaluation of crack resistance
Each test sample is cut with general knife, is then carried out using cellophane tape on the solder mask close to cut surface Peel test.Solder mask is observed after peel test.Evaluation of result is as follows.
A：Crackle is not observed in solder mask, and after peel test is carried out using cellophane tape, welding resistance Layer is unstripped.
B：Slight crackle is observed in solder mask, but after peel test is carried out using cellophane tape, welding resistance Layer is unstripped.
C：A large amount of crackles are observed in solder mask, but after peel test is carried out using cellophane tape, solder mask It is unstripped.
D：After peel test is carried out using cellophane tape, solder mask is peeled off.
(5) evaluation of glossiness
Using by HORIBA, " each test sample of GLOSS CHECKER " measurements for meeting JIS Z8741 of Ltd. manufactures The measurement angle of solder mask be 60 ° of mirror surface luster.
(6) evaluation of solder heat resistance
Weldering will be helped (by London Chemical Co., the water-soluble flux of Inc. manufactures) using LONCO 3355-11 Agent is applied in each test sample.Then, each test sample is immersed in 260 DEG C of fusing solder bath 10 seconds, Ran Houyong Water rinses, and this is defined as a process.After the process 3 times is carried out, the appearance of solder mask is observed.Evaluation of result is such as Under.
A：Exception is not observed.
B：It was observed that very slight change.
C：It was observed that slight change.
D：Significant change (such as stripping) is observed in solder mask.
(6) evaluation of hot-cracking resistance
Prepare the printed substrate for including the copper conducting wiring that thickness is 25 μm.With above-mentioned preparation test sample identical Under the conditions of, form solder mask on the printed substrate.
Weldering will be helped (by London Chemical Co., the water-soluble flux of Inc. manufactures) using LONCO 3355-11 Agent applies on solder mask on a printed-wiring board.Then, printed substrate is immersed in 280 DEG C of fusing solder bath 10 seconds, Then rinsed with water, this is defined as a process.After the process 3 times is carried out, the appearance of solder mask is observed.As a result Evaluation is as follows.
A：Crackle (rupture) is not observed in solder mask.
B：Slight crackle is observed in the solder mask of near interface between solder mask and conducting wiring.
C：Crackle is clearly observed in solder mask.
(7) evaluation of resistance to thermochromism
Use immediately after the preparation by KONICA MINOLTA SENSING, the spectrocolorimeter (model of INC. manufactures CM-600d the b* values in the L*a*b* color systems of the solder mask of each test sample) are measured.Then, will be each at 250 DEG C Test sample heats 5 minutes, then measures the b* values of solder mask again.By being subtracted from the b* values of the solder mask after heating The b* values of solder mask before heating carry out calculated value (Δ b*).Evaluation of result is as follows.
A：Δ b* values are less than 2.0.
B：Δ b* values are more than or equal to 2.0 and less than 2.5.
C：Δ b* values are more than or equal to 2.5 and less than 4.0.
B：Δ b* values are more than or equal to 4.0.
(8) evaluation of cohesive
It is in accordance with JIS D0202 method of testing, the solder mask of each test sample is crosscutting into checkerboard pattern, enforcement of going forward side by side With the peel test of cellophane tape.The visually solder mask after observation peel test.Evaluation of result is as follows.
A：Change is not observed in all 100 transverse portions.
B：The slight fluctuation of solder mask is observed in one of 100 transverse portions.
C：The stripping of solder mask is observed in 2 to 10 of 100 transverse portions.
D：The stripping of solder mask is observed in 11 to 100 of 100 transverse portions.
(9) evaluation of scratch resistance
The angle for the copper-clad laminate for being 10cm × 10cm with planar dimension scrapes the solder mask of each test sample.Observe copper Whether adhere on solder mask.Evaluation of result is as follows.
A：Copper is not adhered on solder mask.
B：Striated copper is lightly adhered on solder mask.
C：Striated copper is significantly adhered on solder mask.
The result of above-mentioned evaluation is shown in table 1 below into 4 " evaluation ".
Pay attention to, " the E/A ratios " in table 1 to 4 is the epoxy in all epoxides included in solder mask composition The equivalent of base is with being included containing the ratio between 1 equivalent carboxyl in carboxy resin.In addition, " the YDC percentages " in table 1 to 4 is powder Last shape hydroquinone epoxy compound phase for included in solder mask composition containing carboxy resin, the heat-curable component included and Comprising photopolymerizable component total amount percentage by weight.
[table 1]
[table 2]
[table 3]
[table 4]
Such as from above-mentioned obvious, liquid solder mask agent composition according to the first embodiment of the invention includes containing carboxy resin (A), heat-curable component (B), photopolymerizable component (C) and Photoepolymerizationinitiater initiater (D).Heat-curable component (B) includes epoxy compound Thing (B1).Epoxide (B1) includes the Powder epoxy compound (B11) represented by following formula (1).Relative to tree containing carboxyl The total amount of fat (A), heat-curable component (B) and photopolymerizable component (C), the amount of epoxide (B11) for 2.0 weight % extremely 12.0 weight %.Relative to the carboxyl containing 1 equivalent in carboxy resin (A), the equivalent of epoxide (B1) epoxy group is 1.0 Equivalent is to 4.0 equivalents.
[chemical formula 3]
R in formula (1)1、R2、R3And R4It independently is methyl, hydrogen atom or the tert-butyl group.
In the first embodiment, although liquid solder mask agent composition includes Powder epoxy compound (B11), by liquid The solder mask that the cured product of solder mask composition is formed is also glossiness and can be with the smooth surface of height.
In the liquid solder mask agent composition according to the second embodiment realized with the first combination of embodiment, epoxidation Compound (B1) can also include the epoxide (B12) in addition to epoxide (B11).
In the liquid solder mask agent composition according to the 3rd embodiment realized with the second combination of embodiment, epoxidation Compound (B12) can include the compound of fusing point or softening point greater than or equal to 60 DEG C.
In the 3rd embodiment, the adherence of the coating formed by liquid solder mask agent composition can reduce.
In the liquid solder mask agent according to the 4th embodiment with the second embodiment or the realization of the 3rd combination of embodiment In composition, epoxide (B12) can be included without aromatic compound.
In the 4th embodiment, the resistance to thermochromism of solder mask is improved.
Combined with any one in the first embodiment to the 4th embodiment realize according to the 5th embodiment In liquid solder mask agent composition, liquid solder mask agent composition can include titanium dioxide (E).
In the 5th embodiment, solder mask can obtain extra high light reflectivity.
According to the printed substrate of the 6th embodiment include comprising according to the first embodiment into the 5th embodiment The liquid solder mask agent composition of any one cured product solder mask.
In a sixth embodiment, can obtain including solder mask that is glossiness and there being height smooth surface Printed substrate.

Claims (6)

1. a kind of liquid solder mask agent composition, including：
Containing carboxy resin (A)；
Heat-curable component (B)；
Photopolymerizable component (C)；With
Photoepolymerizationinitiater initiater (D),
The heat-curable component (B) includes epoxide (B1),
The epoxide (B1) includes the Powder epoxy compound (B11) represented by following formula (1),
[chemical formula 1]
R in formula (1)1、R2、R3And R4Methyl, hydrogen atom or the tert-butyl group independently are,
It is described relative to the total amount containing carboxy resin (A), the heat-curable component (B) and the photopolymerizable component (C) The amount of epoxide (B11) be 2.0 weight % to 12.0 weight %, and
Relative to the carboxyl for containing 1 equivalent in carboxy resin (A), the equivalent of epoxide (B1) epoxy group is 1.0 equivalents to 4.0 equivalents.
2. liquid solder mask agent composition according to claim 1, wherein
The epoxide (B1) is also comprising the epoxide (B12) in addition to the epoxide (B11).
3. liquid solder mask agent composition according to claim 2, wherein
The epoxide (B12) includes the compound of fusing point or softening point greater than or equal to 60 DEG C.
4. the liquid solder mask agent composition according to Claims 2 or 3, wherein
The epoxide (B12) is included without aromatic compound.
5. liquid solder mask agent composition according to any one of claim 1 to 4 also includes titanium dioxide (E).
6. a kind of printed substrate, including include liquid solder mask agent composition according to any one of claim 1 to 5 The solder mask of cured product.
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